TW201035241A - Resin composition and display device using the same - Google Patents

Abstract

The present invention provides a resin composition comprising (a) polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor; (b) 1,5-dihydroxynaphth naphthalene, 1,6- dihydroxynaphth naphthalene, 1,7- dihydroxynaphth naphthalene, or 2,3- dihydroxynaphth naphthalene; and c a hot crosslink agent with specific structure. In view of the resin composition of the present invention, the resin composition is capable of keeping transmittance of the resin film before curing, at the same time, it capable of reducing transmittance of the curing film in the visible light region.

Description

201035241 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a resin composition. More specifically, it relates to a resin composition which is suitable for a surface protective film or an interlayer insulating film of a semiconductor element, and an insulating layer of an organic electroluminescence (Electroluminescence: EL) element, and a display using an organic EL element. A thin film transistor for driving a device (Thin Film Transistor: hereinafter referred to as TFT) q a planarization film of a substrate, a wiring protective insulating film for a circuit board, on-chip microlens of a solid-state imaging device, or various displays, Uses for flattening films for solid-state imaging devices, solder resists for circuit boards, and the like. [Prior Art] A cured film obtained by curing a composition containing polyimine or polybenzoxazole is widely used for an insulating film, a protective film, a planarizing film, or the like of a semiconductor element or a display device. In particular, in the case of a display device, for example, in the use of an insulating layer of an organic EL display or a black matrix of a liquid crystal display, it is required to lower the transmittance of the cured film in order to improve the contrast. Further, in order to prevent malfunction due to light entering the driving TFT of the display device or leakage current, it is also required for the insulating layer of the organic EL display or the planarizing film provided on the TFT substrate of the organic EL display. Reduce the transmittance. In the cured film, as a technique for lowering the transmittance of a visible light region having a wavelength greater than 400 nm, for example, a black matrix material for a liquid crystal display or an RGB paste material, etc., it is possible to add carbon black or a resin composition. A method of a coloring agent for organic, inorganic pigments, dyes, and the like. Since the resin composition containing the 201035241 toner has absorption in an exposed region of 400 to 45 nm, it is difficult to use a positive photosensitive resin composition which is photo-sensitized to reach the bottom of the film. A negative photosensitive resin composition which is a photocuring film from the surface is used. In the positive-type photosensitive resin composition, a technique of reducing the transmittance of the cured film is, for example, a positive-type radioactive resin composition (for example, see Patent Document 1), which contains an alkali-soluble resin, a quinonediazide compound, and a colorless color. a coloring composition such as a coloring material and a color developing agent; a photosensitive resin (for example, refer to Patent Document 2), which is a heat sensitive material which is black when heated; and a positive photosensitive resin composition (for example, refer to Patent Document 3), which contains an alkali-soluble resin, a quinonediazide compound, a color-developing compound which is colored by heating and exhibits absorption greatly at 350 nm or more and 700 nm or less, and 3 A compound which absorbs a maximum of 50 nm or more and less than 500 nm does not exhibit a maximum absorption, and exhibits an absorption maximum of 500 nm or more and 750 nm or less. By using a chromonic compound which is colored by energy such as heat, it is possible to lower the transmittance of the cured film while maintaining the transmittance of the resin film before curing in the exposure wavelength region. technology. Therefore, it is possible to impart sensitivity to both the positive and negative types of the resin composition, and the versatility is high. CITATION LIST Patent Literature Patent Literature 1: JP-A-2008-122501 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei No. Hei. Contents to be Solved by the Invention The color-developing compound itself undergoes an intramolecular structural change due to heat, and exhibits an absorption in a specific wavelength region. Recently, in order to further improve the general versatility, it is desirable to have a resin composition which can exhibit absorption in the exposure wavelength region by other means not only by a color-developing compound. Accordingly, an object of the present invention is to provide a resin composition capable of reducing the transmittance of a hardened film in a visible light region while maintaining a transmittance of a resin film before curing by combining a specific compound. Means for Solving the Problem That is, the present invention is a resin composition characterized by: (a) polyimine, polybenzoxazole, polyimine precursor or polybenzoxazole precursor' b) 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene, and (c) having the structure represented by the following formula (1) The thermal crosslinking agent or Q is a thermal crosslinking agent having a group represented by the following formula (2).

In the above formula (1), R represents a linking group having a valence of 2 to 4. R1 is a monovalent organic group having a carbon number of 1 to 20, Cl, Br, I or F, and R2 and 201035241 R3 are CH2OR5 (R5 represents a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 6). . R4 represents a hydrogen atom, a methyl group or an ethyl group. s represents an integer of 0 to 2, and u represents an integer of 2 to 4. -N(CH2OR6), (H)v (2) In the above formula (2), R6 represents a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 6. The t system represents 1 or 2, and the v system represents 0 or 1. However, t + v is 1 or 2. EFFECT OF THE INVENTION According to the present invention, it is possible to obtain a resin composition capable of reducing the transmittance of the cured film in the visible light region while maintaining the transmittance of the resin film before curing. [Embodiment] The resin composition of the present invention contains: (a) polyimine, polybenzoxazole 'polyimine precursor or polybenzoxazole precursor, (b) 1,5-two Hydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene, and (c) a thermal crosslinking agent having a structure represented by the following formula (1) or A thermal crosslinking agent having a group represented by the following formula (2). When the cured film is colored at 400 to 450 nm by the resin combination (b) component and the component (c) of the component (a), the transmittance in the visible light region can be greatly reduced. Any one of the three components (a) to (c) is difficult, and it is difficult to use a coloring system of 400 to 450 nm as a target. Hereinafter, each component will be described. The resin composition of the present invention contains (a) a polyimine, a polybenzopyrene, a polyimide precursor or a polybenzoxazole precursor. These may also contain two or more types of 201035241, and also include two or more types of repeating units. Polyimine and polybenzoxazole are resins having a cyclic structure of a quinone ring in the main chain. The number of repetitions of the repeating unit is preferably 1 〇. The polyimine can be obtained by reacting a tetracarboxylic acid or a corresponding tetracarboxylic acid dicarboxylic acid dicarboxylic acid diester with a diamine or a corresponding diisocyanate, a methyl hydrazine alkylated diamine or the like, and having a tetracarboxylic acid. Acid residue 〇 residue. For example, it can be obtained by subjecting polyamine (one of the polyimide precursors) for reacting tetracarboxylic dianhydride with a diamine by heat treatment or dehydration ring closure. In the case of heat treatment, a solvent which azeotropes with water may be added. Further, it is also possible to add a weakly acidic carboxylate to heat treatment at a low temperature of 10 ° C or lower. The chemically treated ring-closing catalyst may, for example, be a carboxylic anhydride or a dicyclohexylcarbodiimide water condensing agent or a base such as triethylamine. About the precursor of polyimine. The polybenzoxazole can be obtained by reacting a bisaminophenol compound with a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester or the like, and has an acid residue and a bisaminophenol residue. For example, polyhydroxyguanamine (one of polyphenylene precursors) obtained by reacting a bisphenol compound with a dicarboxylic acid can be dehydrated by heat treatment or chemical treatment. In the heat treatment, it may be added with azeotropy such as m-xylene or water, or an acidic compound may be added and copolymerized at a low temperature of 200 ° C or lower or carbazole 100,000 anhydride, di-, tri-, and diamine to obtain a chemical. The solvent is obtained by using a decarboxylate carboxylic acid or a β-carboxyaminobenzoxazole ring. Line heating 201035241 treatment. Examples of the ring-closing catalyst used in the chemical treatment include phosphoric anhydride, a base, and carbodiimide. The polybenzoxazole precursor system will be described later. In the present invention, from the viewpoint of solubility in an aqueous alkaline solution, the polyimine has an acidic group or an acidic group such as OR7, S03R7, CONR7R8, COOR7, S〇2NR7R8 or the like at a tetracarboxylic acid residue or a diamine residue. Derivatives are preferred as having a hydroxyl group. Further, the polybenzoxazole preferably has an acidic group or an acidic group derivative such as 0R7, S03R7, CONR7R8, COOR7, S02NR7R8 or the like in the dicarboxylic acid residue or the bisaminophenol residue, and has a hydroxyl group as f). good. R7 and R8 represent a hydrogen atom or a monovalent organic group having a carbon number of 1 to 20. Further, the 'acid group' means that when all of R7 or R8 is a hydrogen atom, the acid group derivative means when R7 or R8 contains a monovalent organic group having a carbon number of 1 to 20. In the present invention, as a preferred structure of a tetracarboxylic acid residue of polyimine and a dicarboxylic acid residue of polybenzoxazole (hereinafter referred to as an acid residue), the following structures are mentioned The structure or the hydrogen atom is substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group, a fluorine Q atom, and a chlorine atom in place of 1 to 4 The structure is formed. These two or more types can also be used. 201035241

Ον .0 \/ Ο

^ ^<3〇χ /V^ \^\ ❹

201035241

Ch3

Cf3

-10- 201035241 where j is a direct bond, -coo-, -CONH-, -CH2-, C2H4-, -〇, -C3H6-, -S02_, -s-, -Si(CH3)2-, -0-Si(CH3)2-0-, -C6H4-, -C6H4-O-C6H4-, -C6H4-C3H6_C6H4- or -C6H4C3F6-C6H4-. In the present invention, a preferred structure of a diamine residue of a polyimine and a bisaminobenzoquinone residue of polybenzoxazole (hereinafter referred to as an amine residue) is exemplified. The following structure or the hydrogen atom is substituted with 1 to 4 alkyl groups, fluoroalkyl groups, alkoxy groups, ester groups, nitro groups, cyano groups, fluorine atoms, and chlorine atoms having a carbon number of 1 to 20; The structure is formed. These two or more types can also be used.

-11- 201035241

-12 - 201035241

Rv

OH 〇 recognition, 0^°ηολ>_

NH =0

C00R7

0R7 R7 where J is a direct bond, -COO-, -CONH-, -CH2-, -C2H4-, -〇-, -C3H6-, -S〇2-, -s-, -Si(CH3) 2-, -0-Si(CH3)2-0-, -C6H4-, -C6H4-0-C6H4-, -C6H4-C3H6-C6H4- or _C6H4-C3F6-C6H4^R7 represents a hydrogen atom or a carbon number The organic base for the price of 1~20-1 -13 - 201035241. Among the components (a) used in the present invention, the polyimine precursor and the polybenzoxazole precursor are resins having a guanamine bond in the main chain, and are subjected to dehydration ring closure by heat treatment or chemical treatment. It becomes the aforementioned polyimine and polybenzoxazole. The number of repetitions of the repeating unit is preferably from 10 to 10,000. Examples of the polyimine precursor include polylysine, polyphthalate, polyamidamine, polyisodecimide, and the like, and polyglycolic acid or polyphthalate is preferred. Examples of the polybenzoxazole precursor include polyhydroxyguanamine, polyamine amide, polyamine, polyamidimide, and the like, and polyhydroxyguanamine is preferred. From the solubility in an aqueous alkaline solution, the polyimide precursor and the polybenzoxazole precursor have an acidic group or acidity such as OR7, S03R7, CONR7R8, COOR7, S02NR7R8 or the like at the acid residue or the amine residue. The base derivative is preferred, and it is more preferred to have a hydroxyl group. R7 and R8 represent a hydrogen atom or an organic group having a carbon number of from 1 to 20 carbon atoms. Further, the acidic group means that when all of R7 or R8 are a hydrogen atom, the acidic group derivative means a case where R7 or R8 contains a monovalent D organic group having a carbon number of 1 to 20. The acid component of the acid residue constituting the polyimide precursor and the polybenzoxazole precursor, examples of the dicarboxylic acid include citric acid, isodecanoic acid, diphenyl ether dicarboxylic acid, and bis ( Carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, diphenylketone dicarboxylic acid, triphenyldicarboxylic acid, and the like. Examples of the tricarboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, diphenylethertricarboxylic acid, and biphenyltricarboxylic acid. Examples of the tetracarboxylic acid include pyroic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2 ',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 2,2',3,3'-diphenyl ketone tetracarboxylic acid, 2,2- -14- 201035241 ,1 double (3,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 4 dicarboxypropyl ethyl 4 fluoro s) o 丄 i I bis-base residual benzocarboxylate 3-} 2 2 phenyl bis, benzoyl carboxy carboxy pyridine carboxypyrene 4. 6-, ^ 5) butyl 3 , or 2, acid carboxylic acid, tetra-fragrant, etc., acid carboxytetra-naphthyl ether carboxylic acid ring, acid 4 acid carboxylic acid, 3, carboxytetra 1,2 tetraterpene > 1 naphthalene 0-acid 6-9, 1 竣, 5,4,4 2 3 butyl cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, bicyclo [2.2.1·] heptane tetradecanoic acid, ()bicyclo[3.3.1·] Gengyuan tetradecanoic acid An aliphatic tetracarboxylic acid such as bicyclo [3.1.1·]hept-2-iso-tetraresidic acid, bicyclo[2.2 _2·]octanetetracarboxylic acid or adamantanetetracarboxylic acid. These can also be used in 2 or more types. Further, in the hydrogen atom of the above-exemplified dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid, an acidic group or an acidic group derivative such as OR7, S03R7, C〇NR7R8, COOR7 or S02NR7R8, preferably a hydroxyl group or It is more preferable that the sulfonic acid group, the sulfonylamino group, the sulfonate group or the like is substituted with 1 to 4 pieces. These acids can be used either directly or as anhydrides or active esters. Further, by using a ruthenium atom-containing tetracarboxylic acid such as dimethyl decanedioic acid or 1,3-bis(decanoic acid) tetramethyldioxane, the adhesion to the substrate can be improved or washable. Resistance to oxygen plasma and UV ozone treatment used in the net. The tetracarboxylic acid containing such a halogen atom is preferably from 1 to 30 mol% of the total acid component. Examples of the diamine component constituting the amine residue of the polyimine precursor and the polybenzoxazole precursor include bis-indenyl-amino-4-hydroxyphenyl)hexafluoropropane and bis(3- Amino-4-hydroxyphenyl)indole, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino- Hydroxy-containing -15-201035241 diamine, 3,5, 4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)hydrazine -diaminobenzoic acid, 3-carboxy-4,4'-dicarboxyl-containing diamine, 3-sulfonic acid-4,4'-diaminodiphenylamine, dithiol phenylenediamine, 3 , 4'-diaminodiphenyldiphenyl ether, 3,4'-diaminodiphenylmethane, 4,. methane, 3,4'-diaminodiphenylanthracene, 4,4' -diaminodiaminodiphenyl sulfide, 4,4'-diaminodiphenylthiophenoxy)benzene, benzyne, meta-phenylenediamine, p-benzoic acid, 2,6 -naphthalenediamine, bis(4-aminophenoxyphenyl)nonylphenyl) maple, bis(4-aminophenoxy)biphenyl, bis{4phenyl}ether, 1,4-double (4-Aminophenoxy)benzene, 2,2'-diylbiphenyl, 2,2 -diethyl-4,4'-diaminobiphenyl, 3 diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobimethyl-4,4'-di Aminobiphenyl, 3,3',4,4'-tetramethylbenzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, a hydrogen atom of an aromatic ring As a part, a compound of an alkyl group or a halogen halide, or a cyclohexyldiamine, methylenebiscyclohexyldiamine or the like is used. Further, these diamines may be substituted with a group such as I Br or I having a carbon number of 1 to 10 such as a methyl group, an alkyl group of 10 or a trifluoromethyl group. When two or more kinds of these may be used, the aromatic diamine may be 50% using the entire diamine. Further, the diamine exemplified above may have a hydroxyl group or an acidic group having an OR7, SO:COOR7, S02NR7R8 or the like. For better. The diamine may be directly or as a corresponding sulfonic acid-containing dibasic acid such as an ether such as diisoaminodiphenyl ether or 4,4′-diamine 4′-diaminodiphenyldiphenylphosphonium. '3,4'-ether, 1,4-bis(4-amine5-diamine, 1,5-naphthalene di, bis(3-aminophenoxy-(4-aminophenoxy) dimethyl- 4,4'-diamine, 3-methyl-4,4'-benzene, 2,2,3,3,-tetradiamine or a substituted aryl atom to form a diamine The carbon number such as an aliphatic group is i ft alkyl, F, C1: : It is preferable that heat resistance is 1% or more. 3R7, CONR7R8, : Bio is preferable, and cyanate compound or-16 - 201035241 Trimethyl cleavage of diamines used" and 'as a diamine component by using 1,3 -bis(3-aminopropyl)tetramethyldioxane, 1,3-double (4 A halogen-containing diamine such as an anilino group such as tetramethyldioxane can improve adhesion to a substrate or resistance to oxygen plasma or UV ozone treatment used for washing or the like. Preferably, the diamine is used in an amount of from 1 to 30 mol% of the total diamine component. The end of the polybenzoxazole precursor, which is blocked with a hydroxyl, carboxyl, sulfonic or thiol monoamine, anhydride, hydrazine or monocarboxylic acid, is used as the end of the polybenzoxazole precursor. Two or more of these may be used. By having the above-mentioned group at the resin terminal, the dissolution rate of the resin to the alkaline aqueous solution can be easily adjusted to a preferred range. As a preferred example of the monoamine, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-^hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene , 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3- Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosarric acid, 5-aminosalic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -aminobenzenesulfonic acid '3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-amine Preferred examples of the acid anhydride, monoterpene chlorine, monocarboxylic acid, and mono-active ester compound include decanoic anhydride, maleic anhydride, and nadic acid ( Nadic -17- 201035241 acid), an acid anhydride such as cyclohexanedicarboxylic anhydride or 3-hydroxyindole anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydrothio-7-carboxynaphthalene, 1-hydrothio-6-carboxynaphthalene, 1-hydrogen a monocarboxylic acid such as thio-5-carboxynaphthalene '3-carboxybenzenesulfonic acid or 4-carboxybenzenesulfonic acid; and a monoterpene chlorinated compound obtained by chlorinating the carboxy ruthenium, p-citric acid, citric acid, and cis-butyl The diacids of enedic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-residyl naphthalene, etc. A monoterpene chlorine compound obtained by chlorination of a residue, by reaction of a monoterpene chlorine compound with N-hydroxybenzotriazole or N-hydroxy-5-northene-2,3-dicarboxylimenimine The obtained single active ester compound or the like. The content of the terminal blocking agent of the above-mentioned monoamine, acid anhydride, hydrazine chloride, monocarboxylic acid or the like is 0.1 in terms of the number of added moles of the acid component monomer constituting the acid residue or the diamine component monomer constituting the diamine residue. The range of ~60 mol% is better, preferably 5 to 50 mol%. By setting it as such a range, when a resin composition is apply|coated, the adhesiveness of the ruthenium is appropriate, and the resin composition which has the outstanding film physical property can be obtained. Further, it may have a polymerizable functional group at the terminal of the resin. Examples of the polymerizable functional group include an ethylenically unsaturated bond group, an ethynyl group, a methylol group, an alkoxymethyl group and the like. The blocking agent introduced into the resin can be easily detected by the following method. For example, by dissolving a resin in which a terminal blocking agent is introduced in an acidic solution to decompose into an amine component and an acid component which are constituent units of a resin, and performing gas chromatograph (GC) or NMR measurement, it can be easily Check the blocking agent. Further, the resin into which the terminal blocking agent is introduced can be directly detected by thermal decomposition -18 - 201035241 gas chromatography (PGC) or infrared spectroscopy and 13 C NMR spectroscopy. In the present invention, as the component (a), a polyimine precursor or a polybenzoxazole precursor is preferred, and a polyimine precursor is more preferred. The polyimine precursor is subjected to a ring-shaped ruthenium imidization reaction by a hardening at about 200 ° C, and the polybenzoxazole precursor is hardened at about 300 ° C. Roasting, the hydroxy guanamine site undergoes a closed-loop carbazole reaction, and the chemical resistance is greatly improved. Thereby, the polyimide precursor can obtain chemical resistance at a lower temperature of 0 calcination temperature. Further, a photosensitive resin composition obtained by using these precursor resins having a property of shrinkage during hardening baking can obtain a smooth pattern by firing after obtaining a fine pattern by exposure and development steps. When the insulating film is used as the organic EL element in the forward tapered pattern, the coverage of the upper electrode is excellent, and the disconnection can be prevented to improve the reliability of the element. The resin composition of the present invention may contain an alkali-soluble resin other than the component (a). The alkali-soluble resin is a resin having an acidic group soluble in a base, and specific examples thereof include a radical polymerizable monomer having acrylic acid, a phenol novolac resin, polyhydroxystyrene, polyoxyalkylene or the like. Further, the acidity of the resins can be protected to adjust the alkali solubility. The resin is dissolved in choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, carbonic acid, in addition to the aqueous solution of tetramethylammonium hydroxide. An alkaline aqueous solution such as sodium. These resins may contain two or more kinds, but the ratio of the resin contained in the component (a) is preferably 50% by weight or less. The resin composition of the present invention contains (b) 1,5-dihydroxynaphthalene, 1,6-di-19-201035241 hydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene. These may also contain two or more types. By having two hydroxyl groups, the sensitivity is improved as compared with the case where one hydroxyl group is excellent in alkali visibility. Further, the naphthalene structure of the condensed polycyclic structure has a higher electron density than that of the monocyclic compound, and the electron density of the two hydroxyl groups is further improved, and the electrophilic addition reaction of the ruthenium crosslinking agent can be efficiently produced. In addition, since the conjugated system of π electrons expands in the two directions or more and is easily colored after the formation of the crosslinking reaction, the combination of the thermal crosslinking agent of (c) described below can greatly reduce the cured film. Transmittance in the visible light region. This effect is particularly pronounced when having a hydroxyl group at the 1,5-position, 1,6-position, 1,7-position or 2,3-position. Moreover, by means of a thermal crosslinking agent By crosslinking the component (a), the compound of the component (b) can be fixed to the component (a) having excellent heat resistance, and the chemical resistance of the cured film can be improved. The resin composition of the present invention contains (b) , other than 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene, may also contain other condensed polycyclic aromatic compounds having two or more hydroxyl groups. 〇 as a condensed polycyclic aromatic compound having two or more hydroxyl groups The skeleton structure may, for example, be a carbon condensed bicyclic system of pentalene, anthracene, naphthalene, anthracene, heptene or octene, as-benzodioxime, s-benzodioxime, or Carbon condensed tricyclic system of benzene, decene, anthracene, phenanthrene, anthracene, etc., trindene, fluoranthene, vinegar phenanthrene, vinegar, bismuth subphenylene, east, sun, tetraphene a carbon condensed pentacyclic ring system such as a carbon tetracondensed tetracyclic system, picene, perylene, penfen, pentacene or tetraphenylene, etc. Further, it may be a heterocyclic structure. The heterocyclic ring structure contains a nitrogen, sulfur or oxygen atom in place of the carbon atom of one of the carbon condensed polycyclic aromatic compounds -20- 201035241. Examples of the condensed polycyclic aromatic heterocyclic compound include benzofuran and benzene. a condensed heterobicyclic system such as thiophene, anthracene, benzimidazole, benzothiazole, anthracene, quinoline, isoporphyrin, porphyrin or quinoxaline, dibenzofuran, carbazole, acridine, 1, a condensed heterocyclic ring system such as phenanthroline or the like. The condensed polycyclic aromatic compound having two or more hydroxyl groups has the above examples. It is preferred that a part of the hydrogen atom of the compound of the skeleton is substituted with two or more hydroxyl groups. 0 Specific examples of the condensed polycyclic aromatic compound having two or more hydroxyl groups include 1,4 -dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxys-pipeline, 2,3-dihydroxyquinoline Porphyrin, indole-1,2,10-triol, indole-1,8,9-triol, etc. In the resin composition of the present invention, (b) 1,5-dihydroxynaphthalene, 1,6 The content of dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene is preferably 5 parts by weight or more, and 10 parts by weight or more based on 100 parts by weight of the resin of the component (a). Better. Further, it is preferably 1 part by weight or less, more preferably 1 part by weight or less. When the content of the component (b) is 5 parts by weight or more, the transmittance of the cured film in the visible light region can be further lowered. Further, when the amount is 120 parts by weight or less, the strength of the cured film can be maintained and the water absorption rate can be lowered. Further, when two or more components (a) or (b) are contained, it is preferred that the total amount is in the above range. The resin composition of the present invention contains (c) a thermal crosslinking agent having a structure represented by the following formula (1) or a thermal crosslinking agent having a group represented by the following formula (2). These may also contain two or more types. The thermal crosslinking agent of component (c) is crosslinked to (a) polyimine, polybenzoxazole, polyimine precursor or polybenzoxazole-21 - 201035241 precursor and (b)l , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene are each bonded by the three components of (a), (b), (c), The transmittance in the visible light region can be greatly reduced. Moreover, the chemical resistance of the cured film can be improved by the crosslinking reaction.

In the above formula (1), R represents a 2 to 4 valent linking group, and Ri represents an organic group having a monovalent number of carbon atoms of 1 to 20, cl, Br, I or F, and has a carbon number of 1 to 1. The 20-valent organic group is preferably a hydrocarbon group having a carbon number of 1 to 6 such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group. R2 and R3 represent CH2〇R5 (a R5-based hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). R4 represents a hydrogen atom, a methyl group or an ethyl group. The s system represents an integer of 〇 〇 2, and the 11 system represents an integer of 2 to 4. Plural ruler 1~! ^ Each can be the same or different. Examples of the linking group R are as follows. -22- 201035241 R9 Ic—

C-R11

I R10 s- 〇2

-23- 201035241 In the above formula, 'R9 to R2 7' represents a hydrogen atom, an organic group having a carbon number of 1 or more, Cl, Br, I or h as a carbon number of ^20 organic group' with a methyl group, an ethyl group, and a C group. A group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a benzyl group, a naphthyl group and the like are preferred. -N(CH2〇R6)t(H)v (2) In the above formula (2), 'R6' represents a hydrogen atom or a hydrocarbon group having a carbon number of J. The t system represents 1 or 2, and the V system represents 〇 or 1. {J 〇 1 or 2. In the above formula (1), 'R2 and R3' represent a hot junction CH2OR5 (a hydrogen atom of R5 or a monovalent hydrocarbon 3 having a carbon number of 1 to 6 has an appropriate reactivity and is excellent in storage stability, and R5 is carbon· The monovalent hydrocarbon group is preferred. Further, in the photosensitive resin composition containing a photoacid generator or a light agent, R5 is a methyl or ethyl group as a thermal crosslinking agent represented by the formula (1). The number of functional groups of the agent in one molecule is 4 to 8. When the number of functional groups is less than 4, the resin composition which cannot be kneaded is appropriately colored, and the transmittance of the cured film cannot be lowered. On the other hand, when the number of functional groups is more than 8, It is difficult to maintain the stability of the compound itself or the storage of the resin composition. The purity of the compound having the structure represented by the formula (1) is preferably 85% or more, and the purity is 85% or more. It is excellent in the coloring property after the crosslinking reaction of the resin composition is sufficient, and the visible light transmittance of the cured film can be further reduced. Further, the unreacted amount of the water-absorbing group can be reduced. The monovalent base, cyclopentane ~ 6 of 1 Ϊ is, t + v agent is also known as £). Because [for 1 to 4 polymerization is preferred. There is thermal cross-linking. After hardening, the light-receiving area is obtained. The high-purity stability is reduced by more than 75%. The stability and the permeability of the hard region can be reduced to -24-201035241 to reduce the water absorption of the resin composition. A method of obtaining a high-purity thermal crosslinking agent may be recrystallization, distillation or the like. The purity of the thermal crosslinking agent can be determined by liquid chromatography. Preferred examples of the thermal crosslinking agent having the structure represented by the formula (1) are shown below. Ο ❹

H2Cr-〇CH3 C3H7〇—CH2 OC2H5OH <j)C2H5 -CH,

H,JC—〇CH3 C2H5〇-CH OH H

H2C-〇CH3 〇C2Hg-CH

?C3H7?H (j)C3H7 H20\

h2o—OC3H7 (j)C4H9OH OC4H9 H2C^ /L /CH,

OCH, OH OCH, I I I H2C\/^/CH2

;—och3 c4h9o—ςΗ2

OH HI h2c~〇ch3 c4h9o—ch2 -25- 201035241

In the formula (2), R6 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. Further, from the viewpoint of the stability of the compound or the storage stability of the resin composition, in the photosensitive resin composition containing a photoacid generator or a photopolymerization initiator, R6 is preferably a methyl group or an ethyl group in the compound. The number of (CH2OR6) groups contained is preferably 8 or less. Preferred examples of the thermal crosslinking agent having a group represented by the formula (2) are as follows.

N-CH2OCH3 H3COH2C-NAN-CH2OCH3 h3C〇H2C—n\|-CH2OCH Ν—CH20CH Η h3co och3 h3coh2c-n^n-ch2och3 Ο 〇-< Η n-ch2och2ch3 n-ch2och2ch3 H3CH2COH2C-rj^N-CH2OCH2CH3 H3CH2CO OCH2CH3 h3ch2coh2c h3ch2coh2c

N-CH2OCH3

Ch2och2ch3 lrN-CH2OCH2CH3 O H3COH2C-jJ-CH2h3c〇h2c;^nJCn:i h3coh2c ch2och3 ch2och3

H3coh2c H3COH2C N/CH2OCH: ch2och; h3ch2coh2c-n-ch2och2ch;

H3coh2c-nh H3CH2COHAi h3ch2coh2c rCH2OCH2CH3, CH2OCH2CH3 201035241 (c) The content of the thermal crosslinking agent having the structure represented by the formula (1) or the thermal crosslinking agent having the structure represented by the formula (2) is relative to The resin '(a) component is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. Further, it is preferably 1 part by weight or less, more preferably 5% by weight or less. When the content of the component (c) is 5 parts by weight or more, the transmittance of the cured film in the visible light region can be further lowered. Further, when the amount is 120 parts by weight or less, the strength of the cured film 0 is high and the storage stability of the resin composition is also excellent. Further, in the case where two or more kinds of the component (a) or the component (c) are contained, the total amount is preferably in the above range. The resin composition of the present invention may further contain (d) a photoacid generator, (e) a photopolymerization initiator, and (f) a compound containing two or more ethylenically unsaturated bonds, which can impart a positive or negative type. Photosensitive. When the resin composition of the present invention contains (d) a photoacid generator, an acid is generated in the light-irradiating portion, and the solubility of the light-irradiating portion in the alkaline aqueous solution is increased, and the positive embossing in which the light-irradiating portion is dissolved can be obtained. pattern. In addition, by containing the (d) photoacid generator and the epoxy compound, the acid generated in the light-irradiating portion promotes the reaction of the epoxy compound, whereby a negative-type relief pattern in which the light-irradiating portion is insoluble can be obtained. Examples of the (d) photoacid generator include a quinonediazide compound, a phosphonium salt, an iron salt, a diazo gun salt, an iodine salt, etc., and as a quinonediazide compound, a sulfonate of quinonediazide may be mentioned. The acid is bonded to the polyhydroxy compound by an ester, the sulfonic acid of the quinonediazide is bonded to the polyamine compound sulfonamide, and the sulfonic acid of the quinonediazide is in the polyhydroxypolyamine compound ester bond. Knots and / or sulfonamide bonded and so on. Preferably, the polyhydroxy compound -27 - 201035241 or the polyamine compound is substituted with 50% by mole of the entire functional group by quinonediazide. Further, (d) the photoacid generator may be contained in two or more types, and a highly sensitive photosensitive resin composition can be obtained. In the present invention, the quinonediazide compound is preferably one having a 5-naphthoquinonediazidesulfonyl group and a 4-carotene azide-expanding group. The 4-naphthoquinone diazide sulfonate compound absorbs in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The 5-naphthoquinonediazidesulfonyl ester compound has absorption in the g-ray region of the mercury lamp 0 and is suitable for g-ray exposure. In the present invention, it is preferred to select a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound in accordance with the exposure wavelength. Further, it may contain a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group or a 5-naphthoquinonediazidesulfonyl group in the same molecule, and may also contain 4-naphthoquinone. A diazanesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound. (d) Among the photoacid generators, since the acid component generated by the exposure can be appropriately stabilized, a phosphonium salt, a scale salt or a diazo salt is preferred, and an anthracene salt is preferred. In the present invention, from the viewpoint of high sensitivity, the content of the (d) photoacid generator is preferably 0.01 to 50 parts by weight based on 100 parts by weight of the resin of the component (a). Among them, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. Further, the total amount of the onium salt, the scale salt, and the diazo gun salt is preferably in the range of 0.5 to 20 parts by weight. Further, a sensitizer or the like may be further contained as necessary. Further, when two or more types of component (d) are contained, the total amount of these is preferably in the above range. The photosensitive resin composition of the present invention may further comprise (e) a photopolymerization initiator and (f) a compound containing two or more ethylenically unsaturated bonds. In the light -28-201035241, the living radical generated by the irradiation unit radically polymerizes the ethylenically unsaturated bond, and a negative embossed pattern in which the light-irradiated portion is insoluble can be obtained. Examples of the (e) photopolymerization initiator include diethoxyacetamidine, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 1-( 4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl•(2-hydroxy-2-propyl)one, 1- Hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2-propane-2-(o-ethoxycarbonyl)anthracene, 2-methyl-[4-(methylthio)phenyl]-2-flavor 0 phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenyl ketone, methyl phthalic acid benzoate, 4-phenyl diphenyl ketone, 4,4-dichloro bis Phenyl ketone, hydroxydiphenyl ketone, 4-benzoin-4'-methyl-diphenyl sulfide, alkylated diphenyl ketone, 3,3', 4,4'-tetra (third Butyl peroxycarbonyl)diphenyl ketone, 4-benzylidene-N,N-dimethyl-indole-[2-(1-o-oxy-2-propenyloxy)ethyl]benzene bromide Methanaminium, (4-benzylidene), trimethyl saddle, hydrazine monohydrate, 2-hydroxy-3-(4-benzhydryl) Oxy-N,N,N-trimethyl-1-propylammonium chloride, 2-isopropyl-9-oxothene, 2,4-dimethyl-9-oxopurine Hawthorn, 2,4-diethyl-9-oxosulfonium, 2,4-dichloro-9-oxosulfonium, 2-hydroxy-3-(3,4-dimethyl-9 -Sideoxy-9H-thioxanthene-2-yl-oxy)-N,N,N-trimethyl-1-propylammonium chloride, 2,4,6-trimethylbenzamide Phenyl phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(0-benzamide)], 1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indol-3-yl]-ethanone-1-(0-acetamidine), 2,2'-bis(o-chlorophenyl)-4,5,4' , 5'-tetraphenyl-1,2-diimidazole, 10-butyl-2-chloroacridone, 2-ethyl hydrazine, benzoin, 9, 10-phenanthrene - 201035241 醌, camphor , methylphenylglyoxylate, π 5 ·cyclopentadienyl-η6-isopropylphenyl-iron (1+)-hexafluorophosphate ο-), diphenylsulfate derivative, double (η5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1Η-pyrrol-1-yl)-phenyl)titanium, 4,4-bis(dimethylamine) Diphenyl ketone, 4,4 bis(diethylamino)diphenyl ketone ' 9 -oxopurine til哔, 2 - Methyl-9-oxosulfuryl-indole, 2-chloro-9-oxosulfuryl-indole, 4-benzylidene-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethyl Oxyethyl benzene, 2,2-dimethoxy-2-phenyl-2-phenyl acetophenone, 2-carbyl-2-methylpropenylbenzene, p-tert-butyldichloroethane Toluene, benzyl methoxyethyl acetal, hydrazine, 2-tert-butyl fluorene, 2-amino hydrazine,/5-chloropurine, anthrone, benzoxanone, dibenzo Cycloheptanone, methylene fluorenone, 4-azidobenzylidene benzene, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene) )-4-methylcyclohexanone, 2-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)anthracene, 1,3-diphenylpropanetrione-2-(o-B Oxycarbonyl) anthracene, naphthalenesulfonium chloride, quinoline sulfonium chloride, N-phenylphenylthioacridone, 4,4-azobisisobutyronitrile, benzothiazole disulfide, triphenylphosphine A combination of a photoreducible coloring material such as carbon tetrabromide, tribromophenyl maple, benzoyl peroxide, eosin or methylene blue, and a reducing agent such as ascorbic acid or triethanolamine. These may also contain two or more types. In the present invention, (the content of the photopolymerization initiator is preferably from 1 to 20 parts by weight based on 1 part by weight of the resin of the component (a). When 0.1 part by weight or more, it is sufficient by light irradiation. In addition, when the amount is less than 20 parts by weight, 'there is no excessive radical generation, and the light is not irradiated, and the alkali developability is improved. When two or more types of (e) components are contained, The total amount of these is preferably in the above range. (f) A compound containing two or more ethylenically unsaturated bonds, and 201035241 may be ethylene glycol dimethacrylate or ethylene glycol diacrylate. Diethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated bisphenol A dimethacrylate, glycerol dimethacrylate, tri-propylene glycol dimethacrylate, D Diol dimethacrylate, glyceryl triacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated neopentyl alcohol tetraacrylate Ethoxylated iso-cyanuric acid triacrylate, etc. Acrylic monomer. These may also be ¢) containing two or more kinds. In the present invention, (f) the content of the compound containing two or more ethylenically unsaturated bonds is preferably 1 part by weight or more, and more preferably 5 parts by weight or more based on 1 part by weight of the resin of the component (a). Better. Further, it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less. Further, when two or more kinds of the component (f) are contained, the total amount of these is preferably in the above range. Further, in order to adjust the solubility and the like, the resin of the component (a) may be contained in an amount of 1 to 50 parts by weight per 1 part by weight of the compound having only one ethylenically unsaturated 0 bond. Such a compound may, for example, be acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethyl acrylamide, methacrylic acid Methylaminoethyl ester, propylene sulfhydryl porphyrin, 1-hydroxyethyl α-chloroacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl α-chloroacrylate, A 1-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, hydroxypropyl α-chloroacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl α-chloroacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 〇:-chloroacrylic acid 3-hydroxypropyl-31 - 201035241 ester, 1-hydroxy-1-methyl methacrylate, 1-hydroxy acrylate 1-methylethyl ester, 1-hydroxy-indole-methyl ethyl chloroacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-hydroxy-1-methylethyl acrylate, ct-chloroacrylic acid 2-hydroxy-1-methylethyl ester, 1-hydroxybutyl methacrylate, 1-hydroxybutyl acrylate, α-chloroacrylic acid 1-hydroxyl Butyl ester, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, chloroacrylic acid 3-0 Hydroxybutyl ester, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl α-chloroacrylate, 1-hydroxy-1-methylpropyl methacrylate, 1-hydroxy-1 acrylate -Methyl propyl ester, 1-hydroxy-1-methylpropyl chloroacrylate, 2-hydroxy-1-methylpropyl methacrylate, 2-hydroxy-1-methylpropyl acrylate, α-chloroacrylic acid 2 -hydroxy-1-methylpropyl ester, 1-hydroxy-2-methylpropyl methacrylate, 1-hydroxy-2-methylpropyl acrylate, hydroxy-2-methylpropyl α-chloroacrylate, 2-Hydroxy-2-methylpropyl methacrylate, 2-hydroxy-2-methylpropyl acrylate, 2-hydroxy-2-methylpropionate α-chloroacrylate, 2-hydroxy-1 methacrylate ,1-dimethylethyl ester, 2-hydroxy-1,1-dimethylethyl acrylate, 2-hydroxy-1,1-dimethylethyl α-chloroacrylate, 1,2-dimethacrylate Hydroxypropyl ester, 1,2-dihydroxypropyl acrylate, ct-chloroacrylic acid 1,2·2 Propyl propyl ester, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2:3-dihydroxypropyl chloroacetate, 2,3-dihydroxy butyl methacrylate Ester, 2,3-dihydroxybutyl acrylate, 2,3-dihydroxybutyl α-chloroacrylate, p-hydroxystyrene, p-isopropenylphenol, phenylethyl methacrylate, phenylethyl acrylate, α- Phenylethyl chloroacrylate, hydrazine-hydroxymethyl propyl decylamine, hydrazine-hydroxymethyl methacrylamide, α-chloropropene-32- 201035241 acid, crotonic acid, 4-pentenoic acid, 5-hexene Acid, 6-heptenoic acid, 7-octenoic acid, 8-decanoic acid, 9-decanoic acid, 10-indole-carbon suspected acid, thirteen-acid diacid, ricinoleic acid, isocyanic acid 2-( Methyl propylene oxime) ethyl ester, isocyanate 2-(propylene methoxy) ethyl ester, isocyanate 2-(α-chloropropenyloxy) ethyl ester, and the like. These may also contain two or more types. The resin composition of the present invention may further contain (g) a thermal acid generator. (g) The thermal acid generator generates an acid by heating after development as described later, and in addition to 0, it can promote the crosslinking reaction of the resin of the component (a) and the thermal crosslinking agent of the component (c), and can also promote (a). The cyclization of the quinone ring and the carbazole ring of the resin of the component. Therefore, the chemical resistance of the cured film is improved, and the film reduction can be reduced. The acid produced by the (g) thermal acid generator is preferably a strong acid, for example, an alkylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid. Acid is preferred. In the present invention, the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the formula (4) or (5), and these may also contain two or more kinds.

In the above formulae (4) and (5), R3G to R3 2 represent a group having a carbon number of 1 to 10 or a monovalent aromatic group having a carbon number of 7 to 12. The alkyl group and the aromatic group may be substituted, and examples of the substituent include an alkyl group and a carbonyl group. -33-201035241 Specific examples of the compound of the formula (4) include the following compounds.

Specific examples of the compound of the formula (5) include the following compounds.

From the viewpoint of further promoting the crosslinking reaction, the content of the (g) thermal acid generator is preferably 0.1 parts by weight or more, more preferably 3% by weight or more, based on 100 parts by weight of the resin of the component (a). 〇. 5 parts by weight or more is more preferable. The other surface is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, even more preferably 1 part by weight or less, from the viewpoint of electrical insulating properties of the cured film. Further, when two or more kinds of (g) components are contained, the total amount of these is preferably in the above range. The resin composition of the present invention may further contain (h) a dip. When the resin composition of the present invention is used as a solder resist for a circuit board, the range of coating and drying by screen printing can be exhibited, and visuotrophy can be exhibited. It has the effect of keeping the pattern at a predetermined size. Moreover, the effect of suppressing shrinkage of thermosetting can also be expected. (h) In the case of the insulating material, for example, calcium carbonate, two 201035241 cerium oxide, aluminum oxide, aluminum nitride, titanium oxide, cerium oxide titanium oxide composite particles, etc., are oxidized by cerium oxide. Titanium and cerium oxide titanium oxide composite particles are preferred. The conductive material may, for example, be gold, silver, copper, nickel, aluminum, carbon or the like, and silver is preferred. These two or more types may be contained according to the use. The content of the (h) dip is preferably in the range of 5 to 500 parts by weight based on 100 parts by weight of the component (a). (h) The number average particle diameter of the dip material is preferably 1 μm or less, more preferably 2 μm or less. In addition, it is preferable to mix two or more kinds of dips of different numbers and average particle diameters from the viewpoint of imparting thixotropy and stress relaxation. Further, by using particles having a number average particle diameter of 100 nm or less, that is, nanoparticles, as the (h) pigment, it is possible to adjust the physical properties such as the refractive index while maintaining the transmittance of light. In particular, by using nanoparticles having a high refractive index, high transmittance and high refractive index can be simultaneously exhibited. By mixing such nanoparticles, it is possible to suitably use a microlens on a wafer as a solid-state imaging element or a low-temperature curable Ο optical film such as a flattening film for a solid-state imaging element. Examples of suitable particles for the above-mentioned object include tin oxide-alumina composite particles, zirconia-alumina composite particles, oxidation pin-yttria composite particles, tin oxide particles, zirconia-tin oxide composite particles, and titanium oxide particles. , tin oxide-oxidized composite particles, oxidized sand-oxidized composite particles, chromium oxide-titanium oxide composite particles, zirconia particles, and the like. Also, other materials may be used to coat the surface of the particles. The particles may be in the form of a powder or a paste, and are preferably in the form of a paste from the viewpoint of easy dispersion or the like. From the viewpoint of transmittance, the number average particle diameter of the nanoparticles is preferably 50 nm or less, more preferably 30 nm or less. - 201035241 The number average particle size of the dip can be determined by various particle counters. Further, the average particle diameter of the nanoparticles can be measured by a gas adsorption method, a dynamic light scattering method, a X-ray small angle scattering method, or a method of directly measuring the particle diameter by a transmission electron microscope. When the particle diameters obtained by these measurement methods have a volume average or a mass average, etc., the particle shape can be assumed to be spherical and converted into a number average molecular weight. In the resin composition of the present invention, it is also possible to contain a thermochromic compound which exhibits a large absorption by heating by a coloring of 350 nm or more and 700 nm or less, or less than 350 nm or less. The 500 nm nanometer showed no absorption of an extremely large organic pigment or dye which was extremely absorbed above 500 nm and below 750 nm. The color development temperature of the thermochromic compound is preferably 120 ° C or more, more preferably 150 ° C or more. When the color development temperature of the thermochromic compound is higher, the heat resistance under high temperature conditions is more excellent, and the color resistance is not deteriorated by irradiation of ultraviolet light-visible light for a long period of time, and the light resistance is excellent. The thermochromic compound may, for example, be a thermosensitive colorant, a pressure sensitive colorant or a hydroxyl group-containing compound having a triarylmethane skeleton. The resin composition of the present invention may also contain an adhesion improver. Examples of the adhesion improver include vinyl trimethoxy decane, vinyl triethoxy decane, epoxy cyclohexylethyl trimethoxy decane, 3-glycidoxypropyl trimethoxy decane, and 3-ring. Oxypropoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-amine A decane coupling agent such as propyltrimethoxydecane, a titanium coupling agent, an aluminum coupling agent, an aromatic amine compound, and an alkoxy group-containing hydrazine compound. These may also contain two or more types. By including these adhesions -36-

201035241 A good agent can improve the adhesion to a base substrate such as ITO, SiO 2 or tantalum nitride when the photosensitive resin film is developed. Moreover, it is resistant to oxygen plasma and UV ozone treatment used for washing or the like. The content of the agent is preferably _! by weight based on 1 part by weight of the resin of the component (a). The resin composition of the present invention may also contain an adhesion improver. The modifier may, for example, be an alkoxydecane-containing aromatic amine compound, an amine compound or an aromatic-free decane compound. More than these skills. By containing these compounds, the adhesion of the hardened core can be improved. Specific examples of the alkoxydecane-containing aromatic amine compound and the fluorene compound are shown below. Further, a compound obtained by reacting an aromatic fluorene-containing alkoxy group oxime compound may be, for example, a compound obtained by reacting an aromatic amine compound with an alkoxy decane compound having an epoxy group, a chloromethyl group or the like. Wait. Sand wafers, which can improve the adhesion improvement ‘ 0 . 1 ～1 0 as the adhesive aromatic 醯 can contain 2 and the base quinone amide compound and can be exemplified

(j)CH3 H2N>li^1^^-〇CH3 h2N OCH3 <j>CH3 1-OCH3 〇CH3

0CH2CH3 ?CHs 乂 A-〇CH2CH3 CH3CONH^^^i-〇CH3 OCH2CH3 OCH3 yCH2CH3 (pCH2CH

Cj)CH2CH3 gas i—〇CH2CH3 HJ OCH2CH3

CH3CONH 9〇h3 i-〇CH3 OCH3 /=\ 丫_2^_ _3 丫 (j)CH3 Cj)CH3

CH3CONH ^rOCH2CH3 CH3CONH· OCH2CH3

Och2ch3 OCH3 OCH3 nh2 〇CH3 -s|-^γΝΗ000Η3 CH3CONH OCH3

NHCOCH3 OCH3 0CH3 (j)CH3 〒CH3 T〇~sr~~fyi 〇ch3 〇ch3 ^53⁄43⁄4^

9CH3 CH3CONHy^_Ii_〇. OCH3 CH3CONH

NHCOCH3 0CH3 〇CH3 -37- 201035241 Examples of the non-aromatic decane compound include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl trichloro decane, and vinyl quinone (Θ-methoxy group). Vinyl decane compound such as ethoxy)decane, 3-methacryloxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, p-styryltrimethoxydecane, 3 a decane compound containing a carbon-carbon unsaturated bond such as methacryloxypropylmethyldimethoxydecane or 3-methylpropenyloxypropylmethyldiethoxydecane. Among these, 0 vinyl trimethoxy decane and vinyl triethoxy decane are preferred. The total content of the alkoxydecane-containing aromatic amine compound, the aromatic guanamine compound or the aromatic-free decane compound is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin of the U) component. The resin composition of the present invention may contain a surfactant, and the adhesion to the substrate can be improved. Fluoride (product name, Sumitomo 3M Co., Ltd.), MEGAFAC (trade name, DIC), and Sulfron (trade name, Asahi Glass Co., Ltd.) are used as the surfactant. Surfactant, KP3 41 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, CHISSO (share) system), POLYFLOW, GRANOL (trade name, Kyoeisha Chemical Co., Ltd.), BYK ( An acrylic polymer surfactant such as BYK-Chemie Co., Ltd., or the like. The resin composition of the present invention preferably contains a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, r-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylammonium. Equivalent aprotic solvents, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propionate, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, etc. -38- 201035241 Esters of ketones, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl propionate An alcohol such as ethyl lactate, methyl lactate, diacetone alcohol or 3-methyl-3-methylbutanol, or an aromatic hydrocarbon such as toluene or xylene. These may also contain two or more types. The content of the solvent is preferably 100 to 2000 parts by weight based on 100 parts by weight of the resin of the component (a). The resin composition of the present invention preferably has a high transmittance of the resin film before curing and a low transmittance of the cured film in the visible light region. That is, the film having a thickness of 3.0 μm preferably has a change in transmittance of 450 nm before and after hardening of 20% or more. Here, the transmittance at 450 nm is an index of the transmittance in the visible light region. More specifically, a film having a thickness of 3.0 μm (before hardening) at a wavelength of 450 nm, and a film before curing, are applied from a resin composition coated on a substrate 'and heat-treated at 120 ° C for 2 minutes. Under the nitrogen flow, the film having a thickness of 3.0 μm (before curing) obtained by heat treatment for 30 minutes at TC for 30 minutes at a wavelength of 45 0 nm has a transmittance change of 20% or more as determined by the following formula. According to the present invention, the amount of change in transmittance can be easily achieved. The amount of change in transmittance (% before transmittance after hardening (%) - transmittance after hardening (%) When the resin composition of the present invention is used as a photosensitive resin The transmittance of the resin film before hardening is preferably higher. Specifically, the transmittance of the resin film before hardening is preferably 70% or more at 450 nm, more preferably 90% or more. The cured film is in the visible light region. The transmittance is preferably lower. Specifically, the transmittance of the cured film at 450 nm is preferably 70% or less, and more preferably 60% or less, 201035241. By reducing the transmittance of the cured film, the present invention is Resin composition used in display device When the film or the insulating layer is planarized, it is possible to prevent malfunction or leakage current caused by light entering the driving TFT. Therefore, the amount of change in transmittance at 450 nm before and after hardening is 20% or more and 100%. In the following, it is more preferable that it is 30% or more and 100% or less. Next, a method of producing the resin composition of the present invention will be described. For example, the components (a) to (c) described above can be used as necessary ( d) The component (h), the heat-generating component, the adhesion improver, the adhesion improver, or the surfactant are dissolved in a solvent to obtain a resin composition. The dissolution method may be stirring or heating. The range is not particularly limited to the performance of the resin composition, and is usually room temperature to 80 ° C. Further, the order of dissolution of each component is not particularly limited, and for example, a method of dissolving a compound having low solubility in order is dissolved. Further, when a surfactant or a part of an adhesion improver is dissolved and dissolved, the component which is likely to generate bubbles is dissolved, and after the other component is dissolved and added at the end, it is possible to prevent other components caused by the generation of bubbles. The resin composition obtained by the ruthenium is preferably filtered by a filter to remove dust or particles. The filter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, or the like, but is not limited thereto. The filter is made of polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc. It is preferably polyethylene or nylon. It is contained in the resin composition (h) In the case of the dip, it is preferable to use a filter having a pore diameter larger than the particle diameter. Hereinafter, a method for producing a cured film using the resin composition of the present invention will be described. The resin composition of the present invention is subjected to a spin coating method, Coating with a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a tree-4U-201035241 lipid composition. It is also possible to pre-treat the coated resin composition in advance using the above-mentioned adhesion improver before coating. For example, the modifier is dissolved in a solvent such as isopropyl alcohol, ethylhydrazine water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monoethyl lactate or diethyl adipate at a concentration of 5 to 20% by weight. The solution into the surface of the material. As a method of treating the surface of the substrate, a method such as slit coating, bar coating, dip coating, spray coating, or ruthenium may be mentioned. The film can be obtained by subjecting the substrate and the adhesion improver to a resin composition obtained by heat treatment by subjecting the base material and the adhesion improver to heat treatment by a heat treatment under reduced pressure, if necessary, for example, at 230 °. C heat treatment for 60 minutes method ~400 °C heat treatment 1 minute ~ 10 hours method; add and soak at room temperature ~100 °c low temperature heat treatment method sound wave or electromagnetic wave treatment, and at room temperature ~ 10 0 When the resin composition of the present invention has photosensitivity, the lipid film is partially irradiated with active light such as ultraviolet rays, and the image liquid is subjected to development processing to obtain a negative type or The positive type embossing uses the insulating film obtained by curing the resin composition of the present invention as an insulating film or a protective film for wiring. For example, a film or a substrate such as an amine or a ceramic is used, and a brush substrate is formed using copper, aluminum or the like. The use of the insulating film or the protective film for the wiring and the protective film for soldering the ground solder. When the resin composition contains the material, it can also be used as the wiring material. ί, methanol, methyl ether, to treat the base by spin-coating steam treatment, followed by 50: row reaction. Hardening:; hardening the catalyst in 120 and hardening the tree by super hardening and using a pattern. In the case of the printed circuit of the present invention, the cured film obtained by curing the resin composition of the present invention is suitable as a substrate, a film, and an insulation having TFTs formed in the following order. The planarization film or layer of the display device of the layer and the display device. The display device having such a configuration includes a liquid crystal display device EL display device, etc. The active matrix display device has TFT and wiring on a glass or the like. The wiring is located on the side of the TFT and is connected to the upper surface of the TFT so as to cover the unevenness, and has a flattening film. Q is provided on the planarizing film with a display element. The display element and the wiring system are formed by a flattening film. The contact hole is connected. Fig. 1 is a cross-sectional view of a TFT substrate on which a flat and insulating layer is formed. On the substrate 6, the bottom gate or the top gate type TFT 1 is arranged in a row. The insulating film 3 is formed to cover the state. Further, under the insulating film 3, a wiring 2 in which the TFT 1 is connected is provided. Further, on the insulating film 3, a hole 7 is provided which opens the wiring 2; And the planarizing film 4 is provided in a state in which it is placed in. The planarizing film 4 is provided with an opening so as to reach the contact 配线 of the wiring 2. Further, the contact hole 7 is passed through the connection hole 2 In the state, an ITO (transparent electrode) 5 is formed on the planarizing film 4. The IT 05 is an electrode of a display element (for example, an organic EL element), and the insulating layer 8 is formed so as to cover the periphery of the IT 05. The organic EL may be a substrate. The top emission type in which the illuminating light is emitted from the opposite side of 6 may be a bottom emission type in which light is taken out from the side of the substrate 6. In this way, an active matrix type organic EL display device in which the TFT 1 is connected is obtained. The TFT 1 is used to drive each organic EL element. Further, the cured film obtained by curing the resin composition of the present invention can be flat-insulated or partially formed by the TFTs of the TFT-type TFT1, and is placed in contact with the buried TFT 3, and the components are also bonded. Energy--I-M4 ί, , -42- 201035241 It is suitable to use a planarizing film or an insulating layer which has a display device in which a TFT substrate, an insulating layer, and a display element are formed in the following order. An organic EL display device or the like is exemplified as the display device having such a configuration. The active matrix display device has a TFT and a wiring on a substrate such as glass, and the wiring is located at a side portion of the TFT and is connected to the TFT. The display element and the wiring system are connected through a contact hole formed in the insulating film. Fig. 2 is a cross-sectional view showing a TFT substrate on which an insulating layer is formed. On the substrate 6, the bottom gate type or the top 0 type TFT 1 is arranged in a matrix, and the insulating film 3 is formed in a state of covering the TFT 1. Further, under the insulating film 3, a wiring 2 in which the TFT 1 is connected is provided. Further, on the insulating film 3, a contact hole 7 is provided in such a manner that the wiring 2 is opened. Further, ITO (transparent electrode) 5 is formed through the contact hole 7 in a state in which the wiring 2 is connected. Here, IT05 is an electrode of a display element (for example, an organic EL element). Further, the insulating layer 8 is formed so as to cover the periphery of the IT05, the step of the TFT, and the wiring. The organic EL element may be a top emission type in which light emitted from the opposite side of the substrate 6 is emitted, or 0 may be a bottom emission type in which light is taken out from the side of the substrate 6. In this way, an active matrix type organic EL display device in which the TFTs 1 are connected to each of the organic EL elements can be obtained. For example, when an organic EL display device using a TFT composed of an oxide semiconductor such as amorphous germanium, microcrystalline germanium or In-Ga-Zn-0 or the like is used, since a relatively high-energy blue light ray enters, There are cases where a leakage current or a photo organic current is generated. Since the cured film obtained from the resin composition of the present invention has an appropriate absorption in the vicinity of 450 nm, by using an insulating layer or a planarizing film or the like in such an organic EL display device, it is possible to prevent a leakage current from occurring at -43 to 201035241, The light induces a current or the like to obtain stable driving and luminescent characteristics. In addition, the cured film obtained by curing the resin composition of the present invention can be suitably used for a surface protective film of a semiconductor element such as an LSI, an interlayer insulating film, an adhesive or a bottom coating for sealing an element in a package, and preventing copper from moving. A coating agent, an on-crystal microlens of a solid-state imaging element, or a display for a flattening film for a solid-state imaging element. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. Further, the evaluation of the resin composition in the examples was carried out in the following manner. (1) Evaluation of Transmittance A resin composition (hereinafter referred to as varnish) was spin-coated on a glass substrate of 5 inches square, and heat-treated at 120 ° C for 2 minutes (prebaking) to produce a film thickness of 3.0. Micron pre-baked film. Further, 'the varnish was spin-coated with a film thickness of 3.0 μm after hardening, and an inert oven INH-21 CD manufactured by Koyo Thermos System was used, and heat treatment was performed under a nitrogen stream (oxygen concentration of 20 ppm or less) and 23 (TC). The film thickness of the pre-baked film and the cured film was measured using SURFCOM 1 400D (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 30 minutes. The prebaked film and cured film obtained in this manner were obtained. The transmission spectrum of a wavelength of 300 nm to 700 nm was measured using an ultraviolet-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation) to measure the transmittance at a wavelength of 450 nm. The transmittance of the baked film and the hardened film after curing is determined by the following formula -44 - 201035241. Transmittance change amount (%) = transmittance before curing (%) - transmittance after curing (%) When the amount of change in transmittance is 20% or more, it is judged to be good, and when it is 30% or more, it is extremely good. (2) Evaluation of Sensitivity The varnishes produced in Examples 4 to 11 and Comparative Examples 5 to 6 were spin-coated on a 6-inch wafer, and then heat-treated with a hot plate (Mark-7) for 30 minutes. A prebaked film having a thickness of 4.0 μm was produced. Prebaking temperature Examples Examples 4 to 9 and Comparative Examples 5 to 6 were 120 °C, and Examples 10 to 11 were 100 °C. The obtained prebaked film was subjected to stepwise exposure at 25 mJ/cm 2 using an i-ray stepper (DSW-8000 manufactured by GCA) using an exposure amount of 0 to 500 mJ/cm 2 . The lines and gaps used for exposure are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 50, 100 microns. Examples 10 to 11 After the exposure, the mixture was heated at 100 ° C for 1 minute. Examples 4 to 9 are after exposure, and Example 1 〇 〜1 1 is heated after exposure to '2 3.8 % by weight of tetramethylammonium ruthenium (TMAH) aqueous solution (Mitsubishi GAS Chemical Co., Ltd., ELM) -D) Development for 60 seconds, followed by rinsing with pure water to obtain a developed film. In the case of a positive varnish, the exposure amount at which the exposed portion is completely dissolved and disappeared is taken as the sensitivity. In the case of a negative varnish, the film thickness of the film after development is measured, and the exposure amount remaining after 90% of the film thickness of the prebaking film is taken as the sensitivity. Further, the film thickness after prebaking and after development was measured using a Lamada Ace STM-602' manufactured by Nippon SCREEN Co., Ltd. and having a refractive index of 1.63. (3) Evaluation of chemical resistance (i) The varnishes produced in Examples 1 to 3 and Comparative Examples 1 to 4 were spin-coated on a 6-45 - 201035241 inch wafer, and hot plate heat was used. A pre-baked film having a thickness of 4.0 μm was produced in 3 minutes. Further, the varnishes produced in Examples 4 to 11 and Comparative Examples 5 to 6 were produced by developing the film in accordance with the method described in the above (2). The obtained prebaked film and the developed film 'manufactured by using a Kosher Thermos System inert oven INH-21CD' under a nitrogen stream (oxygen concentration: 20 ppm or less) and heat treatment at 230 ° C for 30 minutes were used. Hardened film. 0 The obtained cured film was immersed at 70 ° C for 1 〇 in a stripping solution of Tokyo Chemical Industry Co., Ltd. at 0 0 °C. Lambda AceTM-602' manufactured by Nippon SCREEN Co., Ltd. was used, and the film thickness of the cured film before and after the peeling liquid treatment was measured with a refractive index of 1.64 to obtain a film reduction. The film reduction is preferably 0.25 μm or less, preferably 0.15 μm or less, and more preferably 0.1 μm or less. (Π) Using the varnishes produced in Examples 4 to 11 and Comparative Examples 5 to 6, a cured film was produced by the method described in the above (i). The obtained ruthenium hardened film was immersed at 1 〇 6 in Tokyo Toka Chemical Industry Co., Ltd. at 7 ° C for 10 minutes. The cured film after the peeling liquid treatment was observed using a 20-fold optical microscope to evaluate whether or not the pattern was peeled off. The smallest pattern in which the pattern is not peeled off is taken as a residual pattern. The finer the pattern is, the more easily it peels off. When the residual pattern is 20 μm or less, it is judged to be good, and when it is 5 μm or less, it is very good. Synthesis Example 1 Synthesis of a hydroxyl group-containing diamine compound 18.3 g of (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (central) BAHF) was dissolved in 100 ml of acetone, 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Co., Ltd.), and cooled to -15 °C. -46-201035241 Here, a solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzimid chloride (manufactured by Tokyo Chemicals Co., Ltd.) in 100 ml of acetone was added dropwise. After the completion of the dropwise addition, the mixture was stirred at -1 5 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50 °C. 30 g of the obtained white solid was placed in a 300 ml stainless steel autoclave to disperse it in 250 ml of methyl sarcolo and 2 g of 5% palladium-carbon (Wako Pure Chemical Industries Co., Ltd.) system). Here, hydrogen gas was introduced using a balloon, and a reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon did not continue to deflate and the reaction was completed. After completion of the reaction, the palladium compound, which is a catalyst, was removed by filtration, and concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

❾ Synthesis Example 2 Synthesis of quinonediazide compound Under dry nitrogen flow, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.8 g (0.1 mol) of 5-naphthoquinone were obtained. Bismuth sulfonium chloride (manufactured by Toyo Kogyo Co., Ltd., NAC-5) was dissolved in 450 g of 1,4-dioxane and allowed to stand at room temperature. Here, 1 2.6 5 g of triethylamine mixed with 50 g of 1,4-dioxane was dropped in such a manner that it did not exceed 35 ° C in the system. After the dropwise addition, the mixture was stirred at 40 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Subsequently, the precipitate which was precipitated was collected and concentrated, and further washed with 1 liter of 1% -47 - 201035241 hydrochloric acid water. Subsequently, it was further washed twice with 2 liters of water. The precipitate was dried using a vacuum dryer to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 3 Synthesis of Compound (A-1) Containing Oxyl Methyl Group (1) 103.2 g (0.4 mol) of 1,1,1-g (4-hydroxyphenyl)ethane (Honori Chemical Industry ( The product, TrisP-HAP) was dissolved in a solution obtained by dissolving 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of 3 6 to 38 wt% aqueous solution of formalin was added dropwise at 20 to 25 ° C for 2 hours. Subsequently, it was stirred at 20 to 2 5 ° C for 1 hour. Here, 98 g of sulfuric acid and 552 g of water were added for neutralization, and left in this state for 2 days. The needle-like white crystals produced in the solution after being placed in the filtration set were washed with 100 ml of water. The white crystals were dried under vacuum at 50 ° C for 48 hours. The high-speed liquid chromatograph manufactured by Shimadzu Corporation was used, and ODS was used as a column, acetonitrile/water = 70/30 as a developing solvent, and the dried white crystal was analyzed at 254 nm. The starting material system completely disappeared and the purity was 92%. Further, when DMSO-d6 was used as a heavy solvent and analyzed by NMR (manufactured by JEOL Ltd., GX-270), hexamethylolated TrisP-HAP was known. (2) Subsequently, the thus obtained compound was dissolved in 300 ml of -48-201035241 methanol, and 2 g of sulfur was added and stirred at room temperature for 24 hours. To the solution, 15 g of an anionic ion exchange resin (manufactured by Rohm and Hass, AMBER LY ST IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Subsequently, 500 ml of ethyl lactate was added and the methanol was removed by a rotary evaporator to become an ethyl lactate solution. When the solution was allowed to stand at room temperature for 2 days, white crystals were produced. When the obtained white crystal was analyzed by high-speed liquid chromatography, it was found that a hexamethoxymethyl compound (an alkoxymethyl group-containing compound) of 0 TrisP-HAP having a purity of 99% represented by the following formula was obtained. A-1)).

Synthesis Example 4 Synthesis of alkoxymethyl group-containing compound (A-2) (1) In addition to using 169.6 g (0.4 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl) -1)-1-methylethyl]phenyl]ethylidene]bisphenol (Chenzhou Chemical Industry Co., Ltd., TrisP-PA) instead of 103.2 g (0.4 moles of hydroxyphenyl) The white crystals were obtained in the same manner as in Synthesis Example 3 (i) except for the production of the product (Trisp-HAP). When this was analyzed by a high-speed liquid chromatograph in the same manner as in Synthesis Example 3 (丨), it was found that the starting material was completely disappeared, and the purity was 8 8 %. Further, when N M r analysis was carried out in the same manner as in Synthesis Example 3 (1), hexamethylolated TrisP-PA was known from -49 to 201035241. (2) Subsequently, white crystals were obtained in the same manner as in Synthesis Example 3 (2) except that the hexamethylolated TrisP-PA obtained by the above method was used instead of the hexamethylated TrisP-HAP. When the obtained white crystal was analyzed by high-speed liquid chromatography, it was found that a hexamethoxymethyl compound (alkoxymethyl group-containing compound (A) having a purity of 99% of TrisP-PA represented by the following formula was obtained. -2)).

Synthesis Example 5 Synthesis of alkoxymethyl group-containing compound (A-3) (1) In the same manner as in Synthesis Example 3 (1), hexamethylmethylated TrisP-HAP having a purity of 92% was obtained. (2) Subsequently, white crystals were obtained in the same manner as in Synthesis Example 3 (2) except that 300 ml of ethanol was used instead of 300 ml of methanol. When the obtained white crystal was analyzed by high-speed liquid chromatography, an ethoxymethyl compound (alkoxymethyl group-containing compound (A) having a purity of 98% of TrisP-HAP represented by the following formula was obtained. -3)). 201035241

Synthesis Example 6 Synthesis of Adhesion Modifier (B-1) 36.6 g (0_1 mol) of BAHF (manufactured by CENTRAL Co., Ltd.) was dissolved in 100 g of ethyl lactate (made by Musashino Chemical Industry Co., Ltd., EL) . Subsequently, 55.6 g (0.2 mol) of 3-glycidoxypropylpropyltriethoxydecane (KBE-4 03, Shin-Etsu Chemical: 3: manufactured by Kokusai Co., Ltd.) was added to the solution, and at 50 The mixture was stirred at ° C for 6 hours to obtain an adhesion improving agent (B-1). The other thermal crosslinking agents and acid generating agents used in the examples and comparative examples are as follows.

-51- 201035241 h3c, 〇〆

, N〆 'O’ H3C\ C,. ’ 'N

H3c, N丨^^^"^3⁄43⁄455·N,. Entering people, ch5

Ο

H3〇^. Η2〇^,. ’,. ’ MW-30HM

Methyl · MX-270

0 Example 1 Under dry nitrogen flow, 32.9 g (0.09 mol) of BAHF was dissolved in 500 g of N-methylpyrrolidone (NMP). Here, 31.0 g (0_1 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (manufactured by MANAC Co., Ltd., 〇DPA) was simultaneously added with 50 g of NMP, and at 30 Stir at °C for 2 hours. Subsequently, 2.18 g (0.02 mol) of 3-aminophenylhydrazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 4 ° C for 2 hours. Furthermore, 5 g of pyridine (manufactured by Tokyo Chemicals Co., Ltd.) was diluted with toluene (manufactured by Tokyo Chemical Co., Ltd.) and added to the solution, and a cooling tube was attached thereto, and the water was azeotroped together with toluene to be removed to the outside of the system. The temperature of the solution was 12 〇 - 52 - 2010 35241 ° C and maintained for 2 hours, and further reacted at 180 ° C for 2 hours. The temperature of the solution was lowered to room temperature, and the solution was poured into 3 liters of water to obtain a white powder. The powder was collected by filtration and washed three times with water. After washing, the white powder was dried by using a vacuum dryer of 5 (TC) for 72 hours to obtain a polyimine. In 10 g of the polyimine, 4 g of 1,5-dihydroxynaphthalene was added (Tokyo Kasei ( ))), 5 g of the methoxymethyl group-containing compound 0 (A-1) obtained in Synthesis Example 3, and 40 g of r-butyrolactone (manufactured by Mitsubishi Chemical Corporation, GBL) to obtain polyfluorene. A varnish of an amine resin composition. The transmittance of the film before and after curing obtained by using the varnish is 550 nm, which is 9.5 % before hardening and 61% after hardening. Therefore, the transmittance change amount is 34. Further, when the chemical resistance of the cured film was evaluated, the film amount was 〇·1 μm or less, which was very good. Comparative Example 1 In addition to adding 5 g of 2,6-dimethoxymethyl-third A phenol (manufactured by Honshu Chemical Co., Ltd.) was used in the same manner as in Example 1 except that the methoxymethyl group-containing hydrazine compound (A-1) obtained in Synthesis Example 3 was used to obtain a polyimine resin composition. The varnish of the material. The transmittance of the film before and after curing obtained by using the varnish is 96% before curing, and 85% after hardening. Therefore, The amount of change in the rate of change was 11%. Further, when the chemical resistance of the cured film was evaluated, the film system was completely dissolved. Comparative Example 2 In a 500 ml flask, 5 g of 2,2'-azobis(isobutyronitrile) was added. 200 g of tetrahydrofuran (TFT). Subsequently, 35 g of methyl methacrylate (MM), 30 g of t-butyl methacrylate (t-BM) and 35 g of methacrylic acid - 201035241 acid (ΜΑ) were added. After temporarily stirring at room temperature and substituting nitrogen in the flask, the mixture was stirred at room temperature for 40 hours. Here, 300 g of propylene glycol monomethyl ether was added and stirred. After the stirring was completed, the solution was poured into 2 liters of water, and the polymer solid was collected by filtration. The precipitate was further washed three times with 2 liters of water, and the collected polymer solid was dried by a vacuum dryer at 50 ° C for 72 hours to obtain an acrylic resin. The obtained acrylic resin was added. 4 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 g of the alkoxymethyl group-containing compound (A-1) obtained in Synthesis Example 3, and 40 g of propylene glycol monomethyl ether acetate A varnish of an acrylic resin composition obtained from an ester (made by KURARAY Co., Ltd., PMA). The varnish is obtained by using the varnish. The transmittance of the film before and after curing at a temperature of 450 nm is 97% before hardening and 93% after hardening. Therefore, the amount of change in transmittance is 4%. Further, when evaluating the chemical resistance of the cured film, the film The solution was completely dissolved.Example 2 Under a dry nitrogen stream, 57.4 g (0.095 mol) of the hydroxyl-containing diamine obtained in Synthesis Example 1, 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl) ϋ Tetramethyldioxane (SiDA) was dissolved in 200 g of hydrazine. Here, 3 1.0 g (0.1 mol) of hydrazine DPA was added and stirred at 40 ° C for 2 hours. Subsequently, a solution of 7.14 g (0.06 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., DFA) was diluted with 5 g of NMP, and dropped in 1 minute. After the dropwise addition, stirring was continued at 40 ° C for 2 hours. After the end of the stirring, the solution was poured into 2 liters of water, and a precipitate of the polymer solid was collected by filtration. Further, the mixture was washed three times with 2 liters of water, and the collected polymer solid was dried by a vacuum dryer of 5 (TC) for 72 hours to obtain polylysine. 10 g of the obtained polylysine was measured. 2 g of 1,6-dihydroxy-54-201035241 naphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 4 g MW-30HM (manufactured by Sanwa Chemical Co., Ltd.) and dissolved in 20 g of EL, 20 g of GBL The varnish of the composition of the polyimide precursor was obtained. The transmittance of the film before and after curing obtained by using the varnish was 94% before curing, and 40% after hardening. Therefore, the transmittance was changed. The amount of transmission was 54%. The transmission spectrum before and after curing was as shown in Fig. 3. It was found that the transmittance at 400 nm to 550 nm was lowered by hardening, and it was clearly colored in the visible light region. In the case of chemical resistance, the film reduction of 0 is less than 0.1 μm, which is very good. Example 3 In addition to the addition of 1 g of the polyimine powder obtained in Example 1, instead of polylysine, A varnish of a polyimide composition was obtained in the same manner as in Example 2. When evaluated, it was hard. The transmittance of the film before and after is about 95% before hardening and 45% after hardening. Therefore, the change in transmittance is 50%. Also, when the chemical resistance of the cured film is evaluated, the film is reduced to 0.1 μm. In the following, it was very good. 〇Comparative Example 3 A novolak resin composition was obtained in the same manner as in Example 2 except that 10 g of a novolac resin PSF 2808 (manufactured by Kyoei Chemical Co., Ltd.) was used instead of polyglycine. The varnish. When evaluated, the transmittance of the film before and after hardening was 74% before hardening, and 78% after hardening. Therefore, the change in transmittance was 9%. Transmission spectrum before and after hardening As shown in Fig. 4, it was found that in the region of 400 nm or more after hardening, the transmittance was hardly lowered, and it was not colored in the visible light region. Further, when the chemical resistance of the cured film was evaluated, the film system was completely dissolved. - 201035241 Comparative Example 4 Polyhydroxybenzene was obtained in the same manner as in Example 2, except that 10 g of a polyhydroxystyrene resin, MARUKALYN CUR S-2 (trade name, manufactured by Nippon Petrochemical Co., Ltd.) was used instead of polyamic acid. Vinyl composition Paint. When evaluated, the transmittance of the film before and after hardening at 45 nm was 97% before hardening and 91% after hardening. Therefore, the change in transmittance was 6%. In the case of the drug, the film system was completely dissolved. Example 4 In the varnish of Example 1, 4 g of the quinonediazide compound obtained in Synthesis Example 2 was dissolved to obtain a positive photosensitive polyimide resin composition. The varnish was used, and the transmittance of the film before and after hardening, the evaluation of chemical resistance, and the sensitivity evaluation were performed using the obtained varnish. The transmittance at 450 nm was 95% before hardening and 60% after hardening. Therefore, the amount of change in transmittance is 35%. The sensitivity is 150m〗/cm2. The film reduction is 0.10 μm or less. Moreover, the pattern of 10 micrometers or more remains. 1) Example 5 Measurement 1 The polyglycine obtained in Example 2, 4 g of 1,7-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5 g of the alkane obtained in Synthesis Example 4 The oxymethyl compound (A-2), 4 g of the quinonediazide compound obtained in Synthesis Example 2, and dissolved in 20 g of EL and 20 g of GBL to obtain a positive photosensitive polyimide precursor Varnish of the composition. Using the obtained varnish, the transmittance evaluation, chemical resistance evaluation, and sensitivity evaluation of the film before and after curing were performed as described above. The transmittance at 45 nm was 90% before hardening and 59% after hardening. Therefore, the amount of change in transmittance was 31%. The sensitivity is -56- 201035241 15 0mJ/cm2. The membrane reduction was 〇·15 μm. Also, the pattern of 10 μm or more remains. Comparative Example 5 A varnish of a positive photosensitive polyimide precursor was obtained in the same manner as in Example 5 except that 1-naphthol was used instead of 1,7-dihydroxynaphthalene. In the evaluation, the film before and after hardening had a transmittance of 450 nm before the hardening was 90%, and after hardening, it was 77%. Therefore, the amount of change in transmittance is 13.3%. The membrane 0 reduction was 0.20 micron. The sensitivity is 300mJ/cm2. Also, patterns of more than 20 microns remain. Comparative Example 6 A varnish of a positive photosensitive polyimide precursor was obtained in the same manner as in Example 5 except that 2,7-dihydroxynaphthalene was used instead of 1,7-dihydroxynaphthalene. In the evaluation, the film before and after curing had a transmittance of 450 nm, which was 90% before hardening and 74% after hardening. Therefore, the amount of change in transmittance was 16.6%. The membrane reduction was 0.15 microns. The sensitivity is 150mJ/cm2. Also, the pattern on the 10 10 μm remains on the Ο. Example 6 In the varnish of Example 5, 0.5 g of 5-propylsulfonyloxyimino-5H-thiophene-2-methylphenyl-acetonitrile (trade name PAG-103) was further used as a thermal acid generator. A CIBA SPECIALTY CHEMICALS (manufactured by CIBA) was dissolved to obtain a varnish of a positive photosensitive polyimide precursor composition. The obtained varnish was used, and the transmittance evaluation, drug resistance evaluation, and sensitivity evaluation of the film before and after hardening were performed as described above. The transmittance at 450 nm is 90% before hardening and 59% after hardening. Therefore, the amount of change in transmittance is 31%. Min -57- 201035241 The sensitivity is 150mJ/cm2. The membrane reduction is 〇·1 μm. Further, a pattern of 10 μm or more remains. Example 7 The varnish of Example 5 was further dissolved in 5 g of the adhesion improver (Β-1) obtained in Synthesis Example 6 to obtain a varnish of a positive photosensitive polyimide precursor composition. Using the obtained varnish, the transmittance evaluation, chemical resistance evaluation, and sensitivity evaluation of the film before and after curing were performed as described above. The transmittance at 450 0 nm is 90% before hardening and 59% after hardening. Therefore, the amount of change in transmittance was 31%. The sensitivity is 150mJ/cm2. The film reduction is 〇·15 μm or less. Further, pattern retention of 3 μm or more was carried out. Example 8 Measurement 1 The polylysine obtained in Example 2, 4 g of 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5 g of Synthesis Example 4 were measured. The obtained alkoxymethyl group-containing compound (Α-2) and 4 g of the quinonediazide compound obtained in Synthesis Example 2 were dissolved in 20 g of EL and 20 g of GBL to obtain a positive photosensitive polypeptone. A varnish of the imine precursor composition. The obtained varnish was used, and the transmittance evaluation, chemical resistance evaluation, and sensitivity evaluation of the film before and after hardening were carried out as described above. The transmittance at 450 nm is 93% before hardening and 63% after hardening. Therefore, the amount of change in transmittance is 30%. The membrane reduction was 0.15 microns. The sensitivity is 200 mJ/cm2. Moreover, the pattern of 1 〇 micrometer or more remains. Example 9 Under a dry nitrogen stream, '18 gram of BAHF was dissolved in 50 grams of NMP, 26.4 grams (0.3 moles) of propylene glycol methyl ether, and the temperature of the solution was cooled to -1 5 °C ° at this 'with internal temperature is not higher than 〇. 〇 〇 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 A solution prepared by dissolving in 25 g of GBL. After the completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours. After the end of the reaction, the solution was poured into 3 liters of water containing 10% by weight of methanol and a white precipitate was collected. The precipitate was collected by filtration and washed three times with water, and then dried using a vacuum dryer at 50 ° C for 72 hours to obtain polyhydroxy decylamine. 0 10 g of polyhydroxydecalamine, 4 g of 1,5-dihydroxynaphthalene, 2 g of the quinonediazide compound of Synthesis Example 2, 0.5 g of WPAG-3 14 (10 g of EL, 30 g of GBL) A varnish of a positive photosensitive polybenzoxazole precursor composition was obtained by the trade name, Wako Pure Chemical Industries Co., Ltd., and 5 g of MX-2 70. The obtained varnish was used, and the transmittance evaluation, chemical resistance evaluation, and sensitivity evaluation of the film before and after hardening were performed as described above. The transmittance at 450 nm is 92% before hardening and 61% after hardening. Therefore, the amount of change in transmittance is 31%. The membrane reduction was 〇.25 μm. The sensitivity is 16〇111>1/〇1112. Also, 图案 20 microns or more remains. Example 1 10 g of the polyhydroxydecalamine obtained in Example 9, 1.5 g of 1,7-dihydroxynaphthalene, 0.5 g of WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and 0.5 g were used as heat. Acid generator 5-1,4-sulfonyloxyimido-5H-thiophene-2-methylphenyl-acetonitrile (trade name: PAG-103, manufactured by CIBA SPECIALTY CHEMICALS), 2 g MW-30HM dissolved A varnish of a negative photosensitive polybenzoxazole precursor composition was obtained at 40 g of GBL. The obtained varnish was used to evaluate the transmittance of the film before and after the hardening as described above, and the evaluation of the drug resistance and the sensitivity of the -59-201035241. The transmittance at 450 nm is 95% before hardening and 57% after hardening. Therefore, the amount of change in transmittance is 38%. The membrane reduction was 0.25 microns. The sensitivity is 200 mJ/cm2. Also, the pattern remains above 20 microns. Example 1 1 In 10 g of the polyimine obtained in Example 1, 5 g of 1,7-dihydroxynaphthalene and 4 g of the alkoxymethyl group-containing compound 0 (A-3) obtained in Synthesis Example 5 were added. 2 g of ethylene oxide modified bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NKESTER BPE-100), 0.5 g of trimethylolpropane triacrylate, 0.1 g 1,2 -Nindione-1-[4-(phenylthio)-2-(0-benzamide)] (manufactured by CIBA SPECIALTY CHEMICALS), 20 g of EL and 20 g of GBL to obtain negative photosensitive polypeptone A varnish of imine resin. The obtained varnish was used, and the transmittance evaluation, chemical resistance evaluation, and sensitivity evaluation of the film before and after hardening were performed as described above. The transmittance at 450 nm is 94% before hardening and 66% after hardening. Therefore, the amount of change in transmittance is 〇 28%. The membrane reduction was 0.1 micron. The sensitivity is 200 mJ/cm2. Also, patterns of 10 microns or more remain. The compositions and evaluation results of Examples 1 to 1 1 and Comparative Examples 1 to 6 are shown in Tables 1 to 3. -60- 201035241

G r-is Φ Solvent GBL (40 g) EL/GBL (20 g / 20 g) EL/GBL (20 g / 20 g) ''-✓ EL/GBL (20 g / 20 g) EL/GBL ( 20 g / 20 g) EL/GBL (20 g / 20 g) EL / GBL (20 g / 20 g) EL / GBL (20 g / 20 g) Other j 1 1 1 1 PAG-103 (〇 · 5 g Adhesion improver B-1 (0.5 g) 1 ΚΜα ^ -N ii α遛w κ- dbK ώ 1 1 t 1 1 1 1 1 1 Photopolymerization initiator (addition amount) 1 1 1 1 1 1 1 1 1 Problem m axt m Photoacid generator (addition amount) 1 1 1 Synthesis Example 2 (4 g) Synthesis Example 2 (4 g) Synthesis Example 2 (4 g) 1 Synthesis Example 2 (4 g) Synthesis Example 2 (4 g Synthesis Example 2 (2 g) WPAG-314 (0.5 g) Thermal crosslinker (addition amount) A-1 (5 g) MW-30HM (4 g) MW-30HM (4 g) A-1 (5 g) ) A-2 (5g) Α-2 (5g) 1 A-2 (5g) A-2 (5g) MX-270 (5g) S ^ m 11 £i 5 cage 1,5-two Hydroxynaphthalene (4 g) 1,6-dihydroxynaphthalene (2 g) 1,6-dihydroxynaphthalene (2 g) 1,5-dihydroxynaphthalene (4 g) 1,7-dihydroxynaphthalene (4 g) 1,7-dihydroxynaphthalene (4 g) 1,7-dihydroxynaphthalene (4 g) 2,3 dihydroxynaphthalene (4 g) 1,5-dihydroxy (4g) Resin (addition amount) Polyimine (10g) Polyglycine (10g) Polyimine (10g) Polyimine (10g) Polyglycine (10g) Poly Proline (10 g) Guanlan M 2 m - Polyglycine (10 g) Polyhydroxyguanamine (10 g) Example 1 Example 2 1 Example 3 Example 4 Example 5 Example 6 Embodiment 7 Embodiment 8 Embodiment 9

VO 201035241 Resin composition solvent GBL (40 g) EL/GBL (20 g / 20 g) GBL (40 g) 1 ΡΜΑ (40 g) EL/GBL (20 g / 20 g) EL/GBL (20 g / 20 g) EL/GBL (20 g / 20 g) EL/GBL (20 g / 20 g) Other PAG-103 (0.5 g) 1 ~遐w ^ K- 1 11磙fe <c<] |1|粼氍1£ s 翠奖_分分 slightly fc fr氍赃诫1 flip II! 1 1 1 1 1 1 Photopolymerization initiator (addition amount) 1 匾渥£砝J1 tls S ΦέΙ 1 1 1 1 1 1 蘅^刼_| W 氍滕米w WPAG'314 (〇_5 g) 1 t 1 1 1 Synthesis Example 2 (4 g) Synthesis Example 2 (4 g) Thermal crosslinking agent (addition amount) MW-30HM (2 g A-3 (4g) ρπ_ «π Γ Γ ^ ^ 1 1 ΠΙ !ώ ^ Α-1 (5g) MW-30HM (4g) MW-30HM (4g) A-2 (5g) A -2 (5g) |1^ 5 ^ Μ a ^ ^ l|i 5 Sauce 1,7-dihydroxynaphthalene (1_5 g) 1,7-dihydroxynaphthalene (5 g) 1,5-dihydroxynaphthalene ( 4 g) 1,5-dihydroxynaphthalene (4 g) 1,6-dihydroxynaphthalene (2 g) 1,6-dihydroxynaphthalene (2 g) 1-naphthol (4 g) 2,7 dihydroxynaphthalene (5 g) Resin (addition amount) Polyhydroxyguanamine (1 g) Polyimine (10 g) Polyimine (10 g) Acrylic resin (10 g) Novolak resin (10 g) Tip · Compared with poly-proline (10 g) Poly-proline (10 g) Really 10 Example π Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 201035241

[Table 3] Transmittance sensitivity Chemical resistance Transmittance before hardening of 450 nm Hardening after curing at 450 nm Transmittance change at 450 nm Film reduction residual pattern Example 1 95% 61 % 34% _ ^O.lO^m _ Example 2 94% 40% 54% - ^0.10//m _ Example 3 95% 45% 50% ^O.lO/zm Example 4 95% 60% 35 % 150mJ/cm2 ^ΟΛΟμτη ΙΟμχη Example 5 90% 59% 31% 150mJ/cm2 ΙΟβπι Example 6 90% 59% 31% l50mJ/cm2 ^0.10//m ΙΟμνη Example 7 90% 59% 31% 150mJ/cm2 0.15//m 3 βτη Example 8 93% 63% 30% 200 mJ/cm 2 0.15 #m ΙΟβχη Example 9 92% 61% 31% 160 mJ/cm 2 0.25//m 20 μ m Example 10 95% 57% 38% 200 mJ/cm 2 0.25 β m 20 μ m Example 11 94% 66% 28% 200 mJ/cm 2 0.10/m ΙΟμπι Comparative Example 1 96% 85% 11% Total dissolution - Comparative Example 2 97% 93% 4% _ Total dissolution - Comparative Example 3 97% 88% 9% Total dissolution Comparative Example 4 97% 91% 6% - Total dissolution _ Comparative Example 5 90% 77% 13% 300 mJ/cm2 0.20 M m 20 μ γη Comparative Example 6 90% 74% 16 % 150mJ/cm2 0Λ5 βτα 10/im Example 1 2 Formed on a glass substrate The bottom gate type TFT is formed and connected to the TFT wiring (having a height of 1.0 μm). An insulating film made of Si3N4 is formed in a state of covering the TFT and the wiring. Subsequently, a contact hole is formed in the insulating film. Further, in order to planarize the unevenness of the TFT and the wiring, a planarizing film is formed on the insulating film. Forming a planarizing film on the insulating film is a varnish of the photosensitive polyimide precursor precursor composition obtained in Example 5 by a coating method on the substrate by -63 - 201035241, and on a hot plate at 12 (TC pre- After baking for 3 minutes, it was exposed, developed, and heated and calcined at 250 ° C for 60 minutes under air flow. The coating property was good when the varnish was applied, and it was confirmed that it was obtained after exposure, development, and baking. The cured film did not produce crepe or cracks. Further, the average section difference of the wiring was 500 nm, and the film thickness of the produced planarizing film was 2000 nm. Subsequently, a top emission was formed on the obtained planarized film. A type of organic EL device. First, a planarizing film is passed through a contact hole to connect f) wiring, and a lower electrode made of ITO is formed by sputtering. Subsequently, the photoresist is coated and pre-baked, and exposed and developed through a desired mask. The photoresist pattern was used as a mask, and patterning was performed by wet etching using an ITO etchant. Subsequently, the photoresist pattern was peeled off using a photoresist stripping solution (a mixture of monoethanolamine and DM SO). The lower electrode obtained in this manner corresponds to the anode of the organic EL device. Subsequently, an insulating layer is formed in such a manner as to cover the periphery of the lower electrode. The varnish of the photosensitive polyimide intermediate precursor composition obtained in Example 5 was similarly used for the absolute Q layer. By providing the insulating layer, it is possible to prevent a short circuit between the lower electrode and the upper electrode formed in the subsequent step. The insulating layer was patterned and heat-treated at 250 ° C for 60 minutes to form an insulating layer having an appropriate absorption near 450 nm. Further, the positive hole transport layer, the red, green, and blue organic light-emitting layers and the electron transport layer are vapor-deposited in the vacuum vapor deposition apparatus through a desired pattern mask. Subsequently, an upper electrode of -64 - 201035241 composed of A1 is formed over the substrate. This corresponds to the cathode of the organic EL element. The obtained substrate was taken out from the smelting machine, and sealed with a sealing glass substrate and an ultraviolet curable epoxy resin. As described above, an active matrix type organic EL display device constituted by connecting TFTs for driving the respective organic EL elements can be obtained. When a voltage is applied through the driving circuit, good light emission is exhibited. Example 1 3 On the glass substrate, a bottom gate type T F T was formed, and a wiring (a height of 1.0 μm) connected to the TFT was formed. An insulating film made of Si3N4 is formed to cover the TFT and the wiring. Subsequently, a contact hole is formed in the insulating film. This wiring is used to connect the organic EL elements and TFTs formed between the TFTs or the subsequent steps. Subsequently, the wiring is connected through the contact hole, and the lower electrode composed of I TO is formed by sputtering. Subsequently, the photoresist is coated and pre-baked, and exposed and developed through a desired mask. This photoresist pattern was used as a mask to perform pattern processing by wet etching using an ITO etchant. Subsequently, the photoresist pattern was peeled off using a photoresist stripping solution (a mixture of monoethanolamine and DMSO). The lower electrode obtained in this manner corresponds to the anode of the organic EL element. Subsequently, an insulating layer was formed so as to cover the periphery of the lower electrode, the TF T and the step of the wiring, and the insulating layer was similarly applied to the varnish of the photosensitive polyimide intermediate precursor composition obtained in Example 5 on the substrate. Thereafter, it was dried under reduced pressure, and prebaked at 120 ° C for 3 minutes by a hot plate, subjected to exposure to 201035241, developed, and subjected to a heat baking treatment at 250 ° C for 60 minutes under a nitrogen gas flow. When the varnish was spin-coated, the coating property was good, and it was confirmed that the cured film obtained after exposure, development, and baking did not cause crepe or cracks. Further, the average section difference of the wiring was 500 nm, and the film thickness of the produced planarizing film was 2000 nm. By providing the insulating layer, it is possible to prevent a short circuit between the lower electrode and the upper electrode formed in the subsequent step. This was carried out to form an insulating layer having an appropriate absorption near 45 nm. Further, in the vacuum vapor deposition apparatus, the positive hole transport layer, the red, green, and blue organic light-emitting layers and the electron transport layer are vapor-deposited in accordance with the pattern mask. Subsequently, an upper electrode composed of A1 is formed over the entire substrate. This corresponds to the cathode of the organic EL element. The obtained substrate was taken out from the vapor deposition machine, and sealed with a sealing glass substrate and an ultraviolet curable epoxy resin. As described above, an active matrix type organic EL display device constituted by connecting TFTs for driving the respective organic EL elements can be obtained. Good light is emitted when a voltage is applied through the drive circuit. Industrial Applicability The resin composition of the present invention is suitable for use in a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer of an organic electric EL element, or a driving thin film transistor substrate using a display device using an organic EL element. Flattening film, wiring protective insulating film for circuit board, on-wafer microlens or various displays for solid-state imaging devices, planarization film for solid-state imaging devices, solder resist for circuit boards, underlying ruthenium, and prevention of copper migration For the use of agents, etc. -bb- 201035241. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a TFT substrate on which a planarizing film and an insulating layer are formed. Fig. 2 is a cross-sectional view showing a TFT substrate on which an insulating layer is formed. Fig. 3 is a transmission spectrum before and after curing of the resin composition of Example 2. Fig. 4 is a transmission spectrum before and after curing of the resin composition of Example 3. [Main component symbol description] 2 3 4 5

TFT wiring Insulation film Planing film ITO substrate Contact hole Insulation layer -67-

Claims (1)

201035241 VII. Patent application scope: 1. A resin composition's characteristics include: (a) polyimine, polybenzoxazole, polyimine precursor or polybenzoxazole precursor, (b l,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,3-dihydroxynaphthalene, and (c) heat having a structure represented by the following formula (1) a crosslinking agent or a thermal crosslinking agent having a group represented by the following formula (2), (In the above formula (1), 'R represents a 2 to 4 valent linking group, R1 represents a monovalent organic group having a carbon number of 1 to 20, Cl, Br, I or F, and R2 and R3 represent CH2OR5. (R5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms), R4 represents a hydrogen atom, a methyl group or an ethyl group, s represents an integer of 0 to 2, and u represents an integer of 2 to 4) -N(CH2OR6)t(H)v (2) (In the above formula (2), R6 represents a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 6, and t represents 1 or 2, v is a system. Indicates 〇 or 1, but t + v is 1 or 2). 2. A positive type photosensitive resin composition which is a resin composition as in the first aspect of the patent application, and further contains (d) a photoacid generator. 201035241 3 . A negative photosensitive resin composition which is a resin composition as in the first aspect of the patent application, further comprising (e) a photopolymerization initiator and (f) having two or more ethylenic unsaturations The compound of the bond. 4. The resin composition according to any one of claims 1 to 3, wherein the film having a thickness of 3 μm or less has a transmittance change of 20 nm or more of a wavelength of 450 nm before and after curing. 5. A device for forming a flattening film obtained by curing a substrate of a thin film transistor and hardening the composition of the tree according to any one of claims 4 to 4, and / or insulating layer; and display components. 6. A display device as claimed in claim 5, wherein the display element is an organic electroluminescent element. -69 -